Method for manufacturing sulphur colors



Patented Nov. 8, 1938 METHOD FOR *MANUFAGTURING" SULPHUR r COLORS Simon Norman,.-Providence, It. I.,. assignor to Industrial Dyestuflr: Company, East.Providence,.,

R.,.I.', acorporation of Rhode Island No-Drawing. Application October '24, 1935,

ScrialNo. 46,629.

14., Claims.

'I'hiscihventionrelates to an improved manufacturezofrsulphur colors bya new method which can: be "used-on alargesvariety of intermediates that :can be. thionated.

Inmanufacturing sulphurwcolors from intermediates, like methyl-hydroxy-aminophenazine and: substituted .diphenylamines and paramidophenoLand. their :homologs, it has been-custom aryto; employ, as thionating agents, alkali metal,

;. polysulphidesror: mixtures. of.sod-aash, sodium sulphide and;sulphur. I have discovered that by theguse' ofr aahottsolution of certain-alkylene amines andusulphur containing substances, sulphurucolorsuare. produced .givingwdifferent shades 11):. andupropertiesaas compared with those obtained whenrusingath'e .=thionating agents; which are at present; being; used 1 in the: manufacture of sulphur colors from thesesame intermediates. As

agspecific' instance, a; hot solution-of diethylene 20,-. diamines and:.sulphur,: or 'homologs' of; same and sulphunrwill produce the. above statedwshadesx In the,followingsexamples; itxsh'ould beunderstood vthat. lnaminot restricted as to temperature;

durationzofitime, or quantitieswused, as various ;,shades. oil-"colors result atv temperaturesrangingv from 110.? C., or even less, up to'200? C.

Itzshoulda: further be: understood thatuwhile more; thereof;

Itzshould; also, beunderstoodathat 'a'wide rangeofstsulphur color intermediates can: be thionated.

bythis :method;

The: alkylene amineswhich .I. use are of the higher: boiling: types, such as; ethylene :-diamine, V tetraethylene triamine, penta ethylene tetra.-. mine, propylene diamine, etc., and their homo IOgStLf Example 1. parts, by weight, ethylene 4.3 diamine are heated at 40 C. with parts sulphur for two hours. parts water are added and then 10 parts phenazine are added. The whole is refluxed for twenty-four hours at 115 C., the mixture is then poured into 1,000 parts 50 water, air is blown in until the dyestufi is precipitated. The dyestufi is then filtered and dried and is now ready for use, giving a red brown shade.

Example 2.-35 parts, by weight, ethylene diamine are heated at 140 C. with 45 parts sul- (CL, 260F129) phur-for two-hours. 50 parts waterare added and then 10 parts-dinitro-para-hydroxy diphen ylamine are added: The whole is refluxedfor twenty-four hours at C;', the --mixture is then poured--intoel,000 parts wat-er, air iskblowrr 5:; in until all the dyestuff'is precipitateds The dyestuif is then filtered and dried and is -nowe ready for use, giving a blue black-shade;

Example 3.35: parts; by Weight, ethylne diamineareheated at C. with 45 parts sul 10 phur for two hours. 50 'parts glycerine are" added and thenlO. parts methylhydroxy-amino-- phenazine are added: Thewhole is refluxed fortwo hours at C.) the mixture-isthen=pouredi into 1,000 parts water, air is blown in -unti l all 162; the dyestuffiis precipitated; Thedyestufi issthen filtered and dried and is now.t-rea'dy-for -use giving a red brown shade.

Example 4-.-45 parts, by weight; tetra-ethylene triamine are heated atw 150 0;? with 45 i; parts' 1s sulphur for two hours, 50 parts' glycerirle arm added and then 10 -parts.paramidopheno-l base; are added; The whole is refluxed 'for two: hours= at 0;, the mixture is then: poured into 1,000 :parts' water, air is. blown in untilall the-flirt dyestufi is precipitated.v The dyestutf is then: filtered and dried and is znowrready fonuse, give ing an olive drab shade.

I claim:

1. The process. of manufacturing. sulphurrcolev 1a ors, which comprises gheating. .451. parts; byiweiglit, of tetra ethylene triamine with 451 partsrby weight; of J'sulphur': atatemperature of about: 150 0., for asperiodofs about 'two .hours,:.adding:.-:

thereto 50 parts,'..by'weight,' ofxglycerine and then; 3.5;;

10. parts; by. weight, ofiparaminophenol base then refluxingrthe .whole. for about? two hours; at; a temperature ofabout 180:C., th'ennpouringi-the mixture into" 1,0 00 parts; by-weightp ofz 'watergx blowing air into the. mixture until all the. dye-w 405 stuffwis precipitated, and: then. filtering-:andidrye ing the said dyestufi.

2. In .a .method OfiiPltBBfiIlllgilSlilDhllI colors from: dyestufi intermediates; :that :are thionateds to produce dyes by means of thionating agents, 45 thionating such dyestuff intermediate selected from a group consisting of amino phenols of the benzene series, amines of the benzene series, and phenazines, in a medium prepared from alkylene amine and sulphur heated together for sub- 50 stantially two hours at substantially 140 to 150 0., in which medium the said dyestuff intermediate is actively converted into a sulphur color.

3. In a method of preparing sulphur colors from dyestufi intermediates that are thionated to 55 produce dyes by means of thionating agents, thionating such dyestufi intermediate selected from a group consisting of amino phenols of the benzene series, amines of the benzene series, and phenazines, in a medium prepared from diethylene diamine and sulphur heated together for substantially two hours at substantially to substantially C., in which medium the said dyestuff intermediate is actively converted into a sulphur color.

4. In a method of preparing sulphur colors from dyestufi intermediates that are thionated to produce dyes by means of thionating agents, thionating such dyestuif intermediate selected from a group consisting of amino phenols of the benzene series, amines of the benzene series, and phenazines, in a medium prepared from tetra ethylene triamine and sulphur heated together for substantially two hours at substantially 140 to substantially 150 C., in which medium the said dyestufi intermediate is actively converted into a sulphur color.

5. In a method of preparing sulphur colors from dyestufi intermediates that are thionated to produce dyes by means of thionating agents, thionating such dyestufi intermediate selected from a group consisting of amino phenols of the benzene series, amines of the benzene series, and phenazines, in a medium substantially identical with that produced by heating together for substantially two hours at substantially the range 140 C.

to 150 C., an alkylene amine, sulphur and a liquid selected from a group consisting of water, glycerine, ethylene glycol, butyl alcohol, amyl al- .cohol, and hexyl alcohol, in which medium the said dyestufi intermediate is actively converted into a sulphur color.

6. In a method of preparing sulphur colors from dyestuff intermediates that are thionated to produce dyes by means of thionating agents, thionating such dyestufi intermediate selected from a group consisting of amino phenols of the benzene series, amines of the benzene series, and phenazines, in a medium substantially identical with that produced by heating together for substan-" tially two hours at substantially the range 140 to 150 C., an alkylene amine, sulphur and higher aliphatic alcohol having more than three carbon atoms, in which medium the said dyestuff intermediate is actively converted into a sulphur color.

7. In a method of preparing sulphur colors from dyestuff intermediates that are thionated to produce dyes by means of thionating agents, thionating such dyestufl intermediate selected from a group consisting of amino phenols of the benzene series, amines of the benzene series, and phenazines, in a medium prepared from propylene diamine and sulphur heated together for substantially two hours at substantially 140 to substantially 150 C., in which medium the said dyestuff intermediate is actively converted into a sulphur color.

8. In a dyestuff, a sulphur color prepared from a sulphur color intermediate selected from a group consisting of amino phenols of the benzene series, amines of the benzene series, and phenazines, thionated in a medium prepared from alkylene amine and sulphur heated together for substantially two hours at substantially the range 140 to 150 C. I

9. In a dyestufi, a sulphur color prepared from a sulphur color intermediate selected from a group consisting of amino phenols of the benzene series, amines of the benzene series, and phenazines, thionated in a medium prepared from a thionating agent and ethylene amine heated together for substantially two hours at substantially the range 140 to 150 C.

10. In a method of preparing sulphur colors from dyestufi intermediates that are thionated to produce dyes by means of thionating agents, thionating such dyestuff intermediate selected from a group consisting of amino phenols of the benzene series, amines of the benzene series, and phenazines, in a medium substantially identical with that produced by heating together for substantially two hours at substantially the range 140 to 150 C., alkylene amine and a thionating agent, in which medium the said dyestufi intermediate is actively converted into a sulphur color.

11. In a method of preparing sulphur colors from dyestuff intermediates that are thionated to producedyes by means of thionating agents, thionating such dyestufi intermediate selected from a group consisting of amino phenols of the benzene series, amines of the benzene series, and

phenazines, in a medium substantially identical with that produced by heating together alkylene amine and sulphur for substantially two hours at substantially 140 to 150 C., in which medium the said dyestuff intermediate is actively converted into a sulphur color.

12. In a dyestufi, a sulphur color prepared from a sulphur color intermediate selected from a group consisting of amino phenols of the benzene series, amines of the benzene series, and phenazines, thionated in a medium substantially identical with that produced by heating together alkylene amine and sulphur for substantially two hours at substantially the range 140 to 150 C.

13. In a dyestuif, a sulphur color prepared from a sulphur color intermediate selected from a group consisting of amino phenols of the benzene series, amines of the benzene series, and phenazines, thionated in a medium prepared from tetra ethylene 'triamine and sulphur heated together for substantially two hours at substantially 140 to 150 C.

'14. In a dyestufi, a sulphur color prepared from a sulphur color intermediate selected from a group consisting of amino phenols of the benzene series, amines of the benzene series, and phenazines, thionated in a medium prepared from propylene diamine and sulphur heated together for substantially two hours at substantially 140 to 

